Vinyl Alcohols. XVI. Reduction of Hindered Diaryl Ketenes by the Grignard Reagent

Abstract

Palmitic Acid (m. p. 62°).-From fractions 1, 2, 3, 4, 5 an acid melting between 56 and 62 0 was obtained. Anilide derivatives prepared from these acids had a m. p. 88.5°. Palmitic acid anilide melts at 89.5°.Stearic Acid (m. p. 69.2°).-No pure stearic acid could be isolated from fractions 3, 4 and 5. After several recrystallizations these fractions yielded products melting at 64, 65 and 67°, respectively, which were mixtures of stearic and palmitic acids. The residue, however, yielded pure stearic acid m. p. 69.2°. An anilide prepared from this acid melted at 93 °. Stearic acid anilide melts at 93 °.

Some New Ideas on Oxidation

“…Condensation reactions requiring acid or base catalysis are assumed to be excluded in neutral oil films. Evidence that per-0-0 I oxides ot the type -C-C-( 37) may be intermediates in drying (44) is not convincing; the "moloxides" which have been reported are probably polymeric peroxides (21,27,28,38).…”

Triphenylethenethiol. Structure, Equilibria with the Thioketone, Solvation, and Association with DMSO

“…Simple enols, defined as enols substituted by hydrogen, alkyl, or aryl groups, but not by strongly electron-withdrawing hydrogen bond-accepting substituents such as carbonyl, are usually much less stable than their carbonyl tautomers . When the double bond substituents are bulky aromatic groups, such as mesityl, the enols are frequently stable, and stability is also enhanced when two β-aryl groups can become coplanar or close to coplanar with the double bond. Appreciable keto ⇌ enol equilibrium constants were determined in these cases, and extensive structural and mechanistic investigations on poly(bulky)aryl-substituted enols were conducted in recent years …”

Simple enols

“…Fuson's Classic Studies Early in this century, there were indications that some simple enols might be isolable. For example, in 1906 Kohler isolated a crystalline compound, mp 95-100 °C, thought to be the enol 2, from conjugate addition of phenylmagnesium bromide to the unsaturated ketone 1.7 The compound, not obtained pure, was Also, certain of these enols (i.e., 7,11,18,22) could be obtained from the corresponding keto forms by acidification of the enolates, or by hydrolysis of the enol esters.…”